The major objective of this study was to determine the chemical structure of long‐chain esters present in lower‐grade olive oil. The classes of esters composing the hexanediethyl ether (99∶1) extract of the wax fraction from a pomace olive oil were: (i) esters of oleic acid with C1−C6 alcohols, (ii) esters of oleic acid with long‐chain aliphatic alcohols in the range C22−C28 and (iii) benzyl alcohol esters of the very long‐chain saturated fatty acids C26 and C28. The analysis and the structure assignments were carried out by gas chromatography coupled with mass spectrometry and by comparison with synthetic authentic model compounds. This work provided precise data on the chemical nature of the wax esters present in olive oil and should represent a means to detect adulteration of higher‐grade olive oil with less expensive pomace olive oil and seed oils.